CN101125808A - A kind of preparation method of anthraquinone and its derivatives - Google Patents

Abstract

The invention relates to a synthesis method of anthraquinone and its derivatives, in particular to a chemical synthesis method for preparing anthraquinone and its derivatives through microwave irradiation and next step reaction in the presence of a catalyst. Phthalic anhydride or substituted phthalic anhydride represented by formula (II) and benzene or substituted benzene represented by formula (III) are ground and mixed in an organic solvent or under solvent-free conditions in the presence of a catalyst , under microwave irradiation with a power of 50-1000W, react at 130-450° C. for 1-120 minutes, and obtain the anthraquinone or its derivatives through separation. The invention has the advantages of simple operation, few reaction steps, environmental friendliness, low production cost, high reaction yield and good industrial applicability.

Description

A kind of preparation method of anthraquinone and its derivatives

(1) Technical field

The invention relates to a preparation method of anthraquinone and derivatives thereof.

(2) Background technology

Prior to the present invention, the existing techniques for chemically synthesizing anthraquinone and its derivatives include naphthoquinone method, anthracene oxidation method and phthalic anhydride method. The naphthoquinone method was developed by the American cyanamide company in the 1950s. This process uses naphthalene as a raw material, which is oxidized into 1,4-naphthoquinone through gas phase oxidation, and then reacts with butadiene to produce tetrahydroanthraquinone through Diels-Alder, and then It can be oxidized into anthraquinone in liquid phase. The production process is mainly based on catalytic reaction, which requires high technology and engineering.

The production of anthraquinone by anthracene oxidation is the main production process of anthraquinone in industrialized countries. It is characterized in that the anthracene separated from coal tar is used as raw material, and anthraquinone is prepared through gas-phase catalytic oxidation. Its reaction formula is as follows:

The characteristic of this process is that there is no three waste pollution, but the main disadvantage is that the method is limited by the source of raw material refined anthracene. Because the anthracene content in coal tar is very low, the process of separating anthracene is very complicated, and the engineering and equipment requirements are high, the price of the obtained refined anthracene is relatively high, and the total cost of producing anthraquinone is also relatively high. This method is the only anthraquinone production method in Germany and the United Kingdom, and Japan still had a part of anthraquinone production from the oxidation method in the 1980s.

The phthalic anhydride method is to condense phthalic anhydride and benzene in the presence of catalysts such as aluminum trichloride to form o-benzoylbenzoic acid, and then dehydrate to generate anthraquinone. Its reaction formula is as follows:

Phthalic anhydride method is the oldest production method of anthraquinone. Its outstanding advantages are sufficient sources of raw materials, low price, simple process flow, no special requirements for equipment, and easy construction and production. Since 1 mol of phthalic anhydride needs to be complexed with 1 mol of aluminum trichloride, and 1 mol of aluminum trichloride needs to be consumed to form a salt with the generated o-benzoylbenzoic acid, a large amount of aluminum trichloride is consumed. And the aluminum trichloride after reaction also can't directly reclaim, after adding water to decompose, all become inorganic aluminum salts and enter waste water system. At the same time, a large amount of sulfuric acid is also required in the closed loop, resulting in waste acid. These two have caused great pressure on the treatment of three wastes.

In recent years, there have been many studies on the synthesis of anthraquinone and its derivatives. In the process of the phthalic anhydride method, most of the research is on the selection and optimization of the catalyst. Chinese invention patent CN97105653.6 provides a method for synthesizing anthraquinone with microwaves. This process uses o-benzoylbenzoic acid as a raw material and bentonite as a catalyst to obtain anthraquinone by ring closure under microwave irradiation. However, this process does not carry out synthesis research under microwaves on the Felck reaction of phthalic anhydride and benzene.

(3) Contents of the invention

The problem to be solved by the present invention is to provide a synthetic method of anthraquinone and its derivatives which is simple in operation, safe and reliable in production, high in reaction yield, low in production cost, and environment-friendly, and overcomes the limitation of anthracene source by the traditional process, the three wastes , complex process and other shortcomings.

The technical scheme that the present invention adopts is as follows:

A kind of preparation method of anthraquinone and derivatives thereof as shown in formula (I), described method is by the phthalic anhydride shown in compound formula (II) or substituted phthalic anhydride and formula (III) The benzene or substituted benzene shown is ground and mixed in an organic solvent or without a solvent in the presence of a catalyst, reacted at 130-450°C for 1-120 minutes under microwave irradiation with a power of 50-1000W, and separated The anthraquinone or its derivatives are obtained. The catalyst is preferably one of the following: aluminum trichloride, zinc chloride, ferric chloride, tin chloride, titanium tetrachloride, sulfuric acid, phosphoric acid, phosphotungstic acid, polyphosphoric acid, nitric acid, boric acid, p-methyl Benzenesulfonic acid.

In formula (I), formula (II), and formula (III), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are each independently hydrogen, hydroxyl, halogen, or sulfonic acid group, mercapto group, mercaptoether group, nitro group, carboxyl group, ester group, cyano group, C1-C5 alkyl group, C1-C5 alkoxy group.

Further, R ₅ , R ₆ , R ₇ , and R ₈ in the compound represented by formula (II) are each independently preferably hydrogen or an electron-withdrawing group such as carboxyl, nitro, sulfonic acid, cyano, halogen, etc.

In the compound represented by formula (III), R ₁ , R ₂ , R ₃ , and R ₄ are each independently preferably hydrogen or an electron-donating group such as hydroxyl, mercapto, mercaptoether, ester, C1-C5 alkyl, C1-C5 alkoxy group, etc.

The amount ratio of the compound represented by the formula (II) to the compound represented by the formula (III) is 1:1.0-1.2.

The amount of the catalyst used is 0.1-10%, preferably 1-5%, of the total weight of the compound represented by the formula (II) and the compound represented by the formula (III).

In the preparation method of the anthraquinone and its derivatives, the mixing method is dissolving and mixing in a solvent, or grinding and mixing without solvent. The organic solvent is DMF (N,N-dimethylformamide), sulfolane, nitrobenzene, glycerin or ethylene glycol. The amount of the organic solvent used is 1 to 5 times, preferably 1 to 3 times, the total weight of the compound represented by formula (II) and formula (III).

Furthermore, in the presence of an organic solvent, the microwave irradiation condition is: irradiation at 130-250° C. for 30-120 minutes. Under solvent-free conditions, the microwave irradiation conditions are: irradiation at 200-450° C. for 1-30 minutes, preferably at 300-400° C. for 5-20 minutes.

The separation step is as follows: after the reaction is completed, ice water is added to stir, then suction filtration, neutralization, stirring, and filtration to obtain the target product anthraquinone or its derivatives.

It is specifically recommended that the described synthetic method be carried out as follows: according to the substance ratio of the compound shown in the formula (II) and the compound shown in the formula (III), it is 1: 1.0～1.2 Feed intake, the catalyst addition is formula (II) 1 to 5% of the total weight of the compound shown and the compound shown in formula (III), dissolved in an organic solvent, mixed uniformly, and reacted at 130 to 250°C for 30 to 120 minutes under microwave irradiation with a power of 50 to 1000W, and the reaction After the end, add ice water and stir, suction filter, add soda ash to neutralize to pH=6.5-7, add sodium hypochlorite solution, stir, filter to obtain the target product anthraquinone or its derivatives; the organic solvent is DMF (N, N- Dimethylformamide), sulfolane, nitrobenzene, glycerol or ethylene glycol, the amount of the organic solvent is 1 to 3 times the total weight of the compound shown in formula (II) and the compound shown in formula (III).

The described synthetic method can also be carried out as follows: according to the substance ratio of the compound shown in the formula (II) and the compound shown in the formula (III) is 1: 1.0～1.2 Feeding, the catalyst addition is formula (II) 1 to 5% of the total weight of the compound shown and the compound shown in formula (III), ground and mixed uniformly under solvent-free conditions, and reacted at 200 to 450°C for 1 to 30 minutes under microwave irradiation with a power of 50 to 1000W, After the reaction, add ice water to stir, filter with suction, add soda ash to neutralize to pH=6.5-7, add sodium hypochlorite solution, stir, and filter to obtain the target product anthraquinone or its derivatives.

The effect of adding hypochlorite in the separation process is to promote the ring closure of unreacted intermediates to generate products.

Compared with the prior art, the preparation method of anthraquinone and its derivatives described in the present invention has the advantages of simple operation, safe and reliable production, high reaction yield, low production cost, environmental friendliness, etc., and has good industrial applicability .

(4) Specific implementation methods:

The technical scheme of the present invention is described below with specific examples, but protection scope of the present invention is not limited thereto:

Example 1

Add 14.8g (0.1mol) of phthalic anhydride (phthalic anhydride), 11.0g (0.1mol) of hydroquinone and 0.25g of aluminum trichloride into the mortar, grind them thoroughly and put them into a 250mL dry flask, put them in Microwave oven, connect the condenser, set the power of the microwave oven to 650W, start the microwave oven, control the reaction temperature 300-350°C, and radiate for 5 minutes. After the reaction is completed, add 50mL of ice water, stir, suction filter, add soda ash to neutralize to pH=6.5 -7, add sodium hypochlorite solution (containing 3.0g of available chlorine), stir, and filter to obtain 22.4g of 1,4-dihydroxyanthraquinone, the yield is 91.5% (calculated as phthalic anhydride, the same below), and the purity is analyzed by high performance liquid chromatography was 98.1%.

Example 2

The feed intake of hydroquinone is 13.2g (0.12mol), the microwave oven power is set to 1000W, and the radiation time is 1 minute. Other operations are the same as in Example 1 to obtain 23.3g of 1,4-dihydroxyanthraquinone, and the yield is 95.3%. , the purity was 98.3% by high performance liquid chromatography.

Example 3

Add 77.4g of DMF (N,N-dimethylformamide) as a solvent, set the power of the microwave oven to 50W, control the reaction temperature to the reflux temperature (about 153°C), the input amount of the catalyst aluminum trichloride is 2.5g, microwave irradiation The time was 120 minutes, and other operations were the same as in Example 1 to obtain 23.5 g of 1,4-dihydroxyanthraquinone with a yield of 96.4% and a purity of 98.5% by high performance liquid chromatography.

Example 4

Change DMF to sulfolane, add 25.8g, set the power of the microwave oven to 100W, control the reaction temperature to 250°C, and microwave irradiation time to 60 minutes. Other operations are the same as in Example 3 to obtain 22.1g of 1,4-dihydroxyanthraquinone , the yield was 88.6%, and the purity by high performance liquid chromatography was 96.2%.

Example 5

Change DMF to sulfolane, add 129.0g, set the power of the microwave oven to 50W, control the reaction temperature to 130°C, and microwave irradiation time to 30 minutes. Other operations are the same as in Example 3 to obtain 23.8g of 1,4-dihydroxyanthraquinone , the yield was 97.8%, and the purity was 98.6% by high performance liquid chromatography.

Example 6

DMF was changed to ethylene glycol, the addition amount was 77.4g, the reaction temperature was reflux temperature (about 200°C), and the microwave irradiation time was 90 minutes. Other operations were the same as in Example 3 to obtain 1,4-dihydroxyanthraquinone 23.2 g, the yield is 94.5%, and the purity analyzed by high performance liquid chromatography is 97.8%.

Example 7

Change DMF to nitrobenzene, the addition amount is 129.0g, the reaction temperature is reflux temperature (about 210°C), and other operations are the same as in Example 4 to obtain 23.6g of 1,4-dihydroxyanthraquinone with a yield of 96.5% , the purity was 98.1% by high performance liquid chromatography.

Example 8

The catalyst was zinc chloride, and the input amount was 1.0 g. Other operations were the same as in Example 1 to obtain 21.6 g of 1,4-dihydroxyanthraquinone with a yield of 88.7%, and a purity of 98.7% through high performance liquid chromatography analysis.

Example 9

The catalyst was polyphosphoric acid, and the input amount was 0.025g. Other operations were the same as in Example 1 to obtain 20.5g of 1,4-dihydroxyanthraquinone with a yield of 83.7%, and a purity of 98.1% through high performance liquid chromatography analysis.

Example 10

The catalyst was boric acid, and the input amount was 2.5g. Other operations were the same as in Example 1 to obtain 22.6g of 1,4-dihydroxyanthraquinone with a yield of 92.4%, and a purity of 98.2% through high performance liquid chromatography analysis.

Example 11

The catalyst is p-toluenesulfonic acid, and the input amount is 1.25g. Other operations are the same as in Example 1 to obtain 22.2g of 1,4-dihydroxyanthraquinone, the yield is 86.8%, and the purity analyzed by high performance liquid chromatography is 93.8%. .

Example 12

The reaction temperature was 400-450° C., and the other operations were the same as in Example 1 to obtain 22.9 g of 1,4-dihydroxyanthraquinone with a yield of 93.8% and a purity of 98.4% by high performance liquid chromatography.

Example 13

The hydroquinone was changed to benzene, and the input amount was 7.8g (0.1mol). Other operations were the same as in Example 1 to obtain 19.8g of anthraquinone, with a yield of 93.8%, and a purity of 98.6% through HPLC analysis.

Example 14

Change hydroquinone into 2-methoxyhydroquinone, input amount is 14.0g (0.1mol), other operation is the same as embodiment 1, obtains 2-methoxy-1,4-dihydroxyanthraquinone 25.5 g, the yield is 91.3%, and the purity analyzed by high performance liquid chromatography is 96.8%.

Example 15

Change hydroquinone into thiophenol, input amount is 11.0g (0.1mol), other operation is the same as embodiment 1, obtains 1-mercaptoanthraquinone 22.4g, yield is 89.2%, through high performance liquid chromatography analysis purity was 95.6%.

Example 16

Change hydroquinone into p-cresol, input amount is 10.8g (0.1mol), control reaction temperature is 200 ℃, microwave irradiation time is 30 minutes, other operation is the same as embodiment 1, obtains 1-hydroxyl-4- Methyl anthraquinone 20.1g, the yield is 80.3%, and the purity analyzed by high performance liquid chromatography is 95.1%.

Example 17

Change hydroquinone into ethyl phenylacetate, input amount is 16.4g (0.1mol), control reaction temperature is 400 ℃, microwave irradiation time is 10 minutes, other operations are the same as embodiment 1, obtain 1-ethyl acetate Anthraquinone was 23.9g, the yield was 76.1%, and the purity was 93.6% through high performance liquid chromatography analysis.

Example 18

Change phthalic anhydride into 3-nitrophthalic anhydride, the input amount is 19.3g (0.1mol), the input amount of aluminum trichloride is 0.34g, other operation is the same as embodiment 1, obtains 1,4 - 26.5 g of dihydroxy-5-nitroanthraquinone, the yield is 90.6%, and the purity analyzed by high performance liquid chromatography is 97.5%.

Example 19

Change phthalic anhydride into 3-chlorophthalic anhydride, the input amount is 18.3g (0.1mol), and the input amount of aluminum trichloride is 0.33g, other operation is the same as embodiment 1, obtains 5-chloro- 23.6 g of 1,4-dihydroxyanthraquinone, the yield was 81.9%, and the purity was 95.3% by high performance liquid chromatography.

Example 20

Change phthalic anhydride into 3-carboxyphthalic anhydride, the input amount is 19.2g (0.1mol), the input amount of aluminum trichloride is 0.33g, other operation is the same as embodiment 1, obtains 1,4- 25.6 g of dihydroxy-5-carboxyanthraquinone, the yield is 81.4%, and the purity analyzed by high performance liquid chromatography is 90.3%.

Example 21

Change phthalic anhydride into 3-sulfonic acid group phthalic anhydride, input amount is 22.8g (0.1mol), the input amount of aluminum trichloride is 0.33g, other operation is the same as embodiment 1, obtains 1, 26.9 g of 4-dihydroxy-5-sulfonic acid anthraquinone, the yield was 76.2%, and the purity by high performance liquid chromatography was 90.6%.

Example 22

Change phthalic anhydride into 3-cyanophthalic anhydride, the input amount is 17.3g (0.1mol), and the input amount of aluminum trichloride is 0.33g, other operation is the same as embodiment 1, obtains 1,4 - 23.6 g of dihydroxy-5-cyanoanthraquinone, the yield is 82.9%, and the purity analyzed by high performance liquid chromatography is 93.1%.

Claims (10)

1. one kind suc as formula the anthraquinone shown in (I) and the preparation method of derivative thereof, it is characterized in that described method is by the Tetra hydro Phthalic anhydride shown in the compound formula (II) or replaces benzene or the substituted benzene shown in Tetra hydro Phthalic anhydride and the formula (III), in the presence of catalyzer, ground and mixed in organic solvent or under the condition of no solvent, at power is under the microwave irradiation of 50～1000W, in 130～450 ℃ of reactions 1～120 minute, obtain described anthraquinone or derivatives thereof through separation; Described catalyzer is one of following: aluminum chloride, zinc chloride, iron(ic) chloride, tin chloride, titanium tetrachloride, sulfuric acid, phosphoric acid, phospho-wolframic acid, polyphosphoric acid, nitric acid, boric acid, p-methyl benzenesulfonic acid;

In formula (I), formula (II), the formula (III), R ₁, R ₂, R ₃, R ₅, R ₅, R ₆, R ₇, R ₈Independent separately is the alkyl of hydrogen, hydroxyl, halogen, sulfonic group, sulfydryl, mercapto ether, nitro, carboxyl, ester group, cyano group, C1～C5 or the alkoxyl group of C1～C5.

2. the preparation method of anthraquinone as claimed in claim 1 and derivative thereof is characterized in that shown in the described formula (II) R in the compound ₅, R ₆, R ₇, R ₈Independent separately is carboxyl, nitro, sulfonic group, cyano group, halogen or hydrogen.

3. the preparation method of anthraquinone as claimed in claim 1 and derivative thereof is characterized in that shown in the described formula (III) R in the compound ₁, R ₂, R ₃, R ₄Independent separately is the alkyl of hydroxyl, sulfydryl, mercapto ether, ester group, hydrogen, C1～C5 or the alkoxyl group of C1～C5.

4. as the preparation method of described anthraquinone of one of claim 1～3 and derivative thereof, it is characterized in that described catalyst levels is 0.1～10% of a compound gross weight shown in compound shown in the formula (II) and the formula (III).

5. as the preparation method of described anthraquinone of one of claim 1～3 and derivative thereof, it is characterized in that described organic solvent is N, dinethylformamide, tetramethylene sulfone, oil of mirbane, glycerine or ethylene glycol.

6. the preparation method of anthraquinone as claimed in claim 5 and derivative thereof is characterized in that described consumption of organic solvent is 1～5 times of compound gross weight shown in compound shown in the formula (II) and the formula (III).

7. as the preparation method of described anthraquinone of one of claim 1～3 and derivative thereof, it is characterized in that in the presence of organic solvent that described microwave irradiation condition is: in 130～250 ℃ of irradiations 30～120 minutes.

8. as the preparation method of described anthraquinone of one of claim 1～3 and derivative thereof, it is characterized in that under condition of no solvent that described microwave irradiation condition is: in 200～450 ℃ of irradiations 1～30 minute.

9. as the preparation method of described anthraquinone of one of claim 1～3 and derivative thereof, it is characterized in that the amount of substance ratio that feeds intake of compound shown in compound shown in the described formula (II) and the formula (III) is 1: 1.0～1.2.

10. as the preparation method of described anthraquinone of one of claim 1～3 and derivative thereof, it is characterized in that described separating step is: react and finish the stirring of back adding frozen water, suction filtration neutralizes then, stirs, and filters and obtains target product anthraquinone or derivatives thereof.